The Composition of Near-solidus Partial Melts of Fertile Peridotite at 1 and 1{middle dot}5 GPa: Implications for the Petrogenesis of MORB

We have determined the near-solidus melt compositions for peridotiteMM-3, a suitable composition for the production of mid-oceanridge basalt (MORB) by decompression partial melting, at 1 and1·5 GPa. At 1 GPa the MM-3 composition has a subsolidusplagioclase-bearing spinel lherzolite assemblage, and a solidusat 1270°C. At only 5°C above the solidus, 4% meltis present as a result of almost complete melting of plagioclase.This melting behaviour in plagioclase lherzolite is predictedfrom simple systems and previous experimental work. The persistenceof plagioclase to > 0·8 GPa is strongly dependenton bulk-rock CaO/Na₂O and normative plagioclase content in theperidotite. At 1·5 GPa the MM-3 composition has a subsolidusspinel lherzolite assemblage, and a solidus at 1350°C.We have determined a near-solidus melt composition at 2% meltingwithin 10°C of the solidus. Near-solidus melts at both 1and 1·5 GPa are nepheline normative, and have low normativediopside contents; also they have the highest TiO₂, Al₂O₃ andNa₂O, and the lowest FeO and Cr₂O₃ contents compared with higherdegree partial melts. Comparison of these near-solidus meltswith primitive MORB glasses, which lie in the olivine-only fieldof crystallization at low pressure, indicate that petrogeneticmodels involving aggregation of near-fractional melts formedduring melting at pressures of 1·5 GPa or less are unlikelyto be correct. In this study we use an experimental approachthat utilizes sintered oxide mix starting materials and peridotitereaction experiments. We also examine some recent studies usingan alternative approach of melt migration into, and entrapmentwithin ‘melt traps’ (olivine, diamond, vitreouscarbon) and discuss optimal procedures for this method. KEY WORDS: experimental petrology; mantle melting; near-solidus; fertile peridotite; MORB     

Origin of the Oceanic Lithosphere

In a global examination of mid-ocean ridge basalt (MORB) glasscompositions, we find that Na₈–Fe₈–depth variationsdo not support modeling of MORBs as aggregates of melt compositionsgenerated over a large range of temperature and pressure. However,the Na₈–Fe₈ variations are consistent with the compositionalsystematics of solidus melts in the plagioclase–spinellherzolite transition in the CaO–MgO–Al₂O₃–SiO₂–Na₂O–FeO(CMASNF) system. For natural compositions, the P–T rangefor melt extraction is estimated to be 1·2–1·5GPa and 1250–1280°C. This P–T range is a closematch with the maximum P–T conditions for explosive pressure-releasevaporization of carbonate-bearing melts. It is proposed thatfracturing of the lithosphere induces explosive formation andescape of CO₂ vapor. This provides the vehicle for extractionof MORBs at a relatively uniform T and P. The upper portionof the CO₂-bearing and slightly melted seismic low-velocityzone flows toward the ridge, rises at the ridge axis to lower-lithospheredepths, melts much more extensively during this rise, and releasesMORB melts to the surface driven by explosively escaping CO₂vapor. The residue and overlying crust produced by this meltingthen migrate away from the ridge axis as new oceanic lithosphere.The entire process of oceanic lithosphere creation involvesonly the upper 140 km. When lithospheric stresses shift fractureformation to other localities, escape of CO₂ ceases, the vehiclefor transporting melt to the surface disappears, and ridgesdie. Inverse correlations of Na₈ vs Fe₈ for MORB glasses areexplained by mantle heterogeneity, and positive variations superimposedon the inverse variations are consistent with progressive extractionof melts from short, ascending melting columns. The uniformlylow temperatures of MORB extraction are not consistent withthe existence of hot plumes on or close to ocean ridges. Inthis modeling, the southern Atlantic mantle from Bouvet to about26°N is relatively homogeneous, whereas the Atlantic mantlenorth of about 26°N shows significant long-range heterogeneity.The mantle between the Charlie Gibbs and Jan Mayen fracturezones is strongly enriched in FeO/MgO, perhaps by a trappedfragment of basaltic crust. Iceland is explained as the productof this enrichment, not a hot plume. The East Pacific Rise,Galapagos Ridge, Gorda Ridge, and Juan de Fuca Ridge samplemantle that is heterogeneous over short distances. The mantlebeneath the Red Sea is enriched in FeO/MgO relative to the mantlebeneath the northern Indian Ocean.     

A modified iterative sandwich method for determination of near-solidus partial melt compositions. II. Application to determination of near-solidus melt compositions of carbonated peridotite

We performed modified iterative sandwich experiments (MISE) to determine the composition of carbonatitic melt generated near the solidus of natural, fertile peridotite + CO₂ at 1,200–1,245°C and 6.6 GPa. Six iterations were performed with natural peridotite (MixKLB-1: Mg# = 89.7) and ∼10 wt% added carbonate to achieve the equilibrium carbonatite composition. Compositions of melts and coexisting minerals converged to a constant composition after the fourth iteration, with the silicate mineral compositions matching those expected at the solidus of carbonated peridotite at 6.6 GPa and 1,230°C, as determined from a sub-solidus experiment with MixKLB-1 peridotite. Partial melts expected from a carbonated lherzolite at a melt fraction of 0.01–0.05% at 6.6 GPa have the composition of sodic iron-bearing dolomitic carbonatite, with molar Ca/(Ca + Mg) of 0.413 ± 0.001, Ca# [100 × molar Ca/(Ca + Mg + Fe*)] of 37.1 ± 0.1, and Mg# of 83.7 ± 0.6. SiO₂, TiO₂ and Al₂O₃ concentrations are 4.1 ± 0.1, 1.0 ± 0.1, and 0.30 ± 0.02 wt%, whereas the Na₂O concentration is 4.0 ± 0.2 wt%. Comparison of our results with other iterative sandwich experiments at lower pressures indicate that near-solidus carbonatite derived from mantle lherzolite become less calcic with increasing pressure. Thus carbonatitic melt percolating through the deep mantle must dissolve cpx from surrounding peridotite and precipitate opx. Significant FeO* and Na₂O concentrations in near solidus carbonatitic partial melt likely account for the ∼150°C lower solidus temperature of natural carbonated peridotite compared to the solidus of synthetic peridotite in the system CMAS + CO₂. The experiments demonstrate that the MISE method can determine the composition of partial melts at very low melt fraction after a small number of iterations.     

Partial melting of secondary pyroxenite at 1 and 1.5 GPa,and its role in upwelling heterogeneous mantle

We performed partial melting experiments at 1 and 1.5 GPa, and 1180–1400 °C, to investigate the melting under mantle conditions of an olivine-websterite (GV10), which represents a natural proxy of secondary (or stage 2) pyroxenite. Its subsolidus mineralogy consists of clinopyroxene, orthopyroxene, olivine and spinel (+garnet at 1.5 GPa). Solidus temperature is located between 1180 and 1200 °C at 1 GPa, and between 1230 and 1250 °C at 1.5 GPa. Orthopyroxene (±garnet), spinel and clinopyroxene are progressively consumed by melting reactions to produce olivine and melt. High coefficient of orthopyroxene in the melting reaction results in relatively high SiO₂ content of low melt fractions. After orthopyroxene exhaustion, melt composition is controlled by the composition of coexisting clinopyroxene. At increasing melt fraction, CaO content of melt increases, whereas Na₂O, Al₂O₃ and TiO₂ behave as incompatible elements. Low Na₂O contents reflect high partition coefficient of Na between clinopyroxene and melt (\(D_{{{\text{Na}}_{ 2} {\text{O}}}}^{{{\text{cpx}}/{\text{liquid}}}}\)). Melting of GV10 produces Quartz- to Hyperstene-normative basaltic melts that differ from peridotitic melts only in terms of lower Na₂O and higher CaO contents. We model the partial melting of mantle sources made of different mixing of secondary pyroxenite and fertile lherzolite in the context of adiabatic oceanic mantle upwelling. At low potential temperatures (T _P < 1310 °C), low-degree melt fractions from secondary pyroxenite react with surrounding peridotite producing orthopyroxene-rich reaction zones (or refertilized peridotite) and refractory clinopyroxene-rich residues. At higher T _P (1310–1430 °C), simultaneous melting of pyroxenite and peridotite produces mixed melts with major element compositions matching those of primitive MORBs. This reinforces the notion that secondary pyroxenite may be potential hidden components in MORB mantle source.     

Carbonatitic melts along the solidus of model lherzolite in the system CaO-MgO-Al2O3-SiO2-CO2 from 3 to 7 GPa

We have experimentally determined the solidus position of model lherzolite in the system CaO-MgO-Al₂O₃-SiO₂-CO₂ (CMAS.CO₂) from 3 to 7 GPa by locating isobaric invariant points where liquid coexists with olivine, orthopyroxene, clinopyroxene, garnet and carbonate. The intersection of two subsolidus reactions at the solidus involving carbonate generates two invariant points, I_1A and I_2A, which mark the transition from CO₂-bearing to dolomite-bearing and dolomite-bearing to magnesite-bearing lherzolite respectively. In CMAS.CO₂, we find I_1A at 2.6 GPa/1230 °C and I_2A at 4.8 GPa/1320 °C. The variation of all phase compositions along the solidus has also been determined. In the pressure range investigated, solidus melts are carbonatitic with SiO₂ contents of <6 wt%, CO₂ contents of ˜45 wt%, and Ca/(Ca+Mg) ratios that range from 0.59 (3 GPa) to 0.45 (7 GPa); compositionally they resemble natural magnesiocarbonatites. Volcanic magnesiocarbonatites may well be an example of the eruption of such melts directly from their mantle source region as evidenced by their diatremic style of activity and lack of associated silicate magmas. Our data in the CMAS.CO₂ system show that in a carbonate-bearing mantle, solidus and near-solidus melts will be CO₂-rich and silica poor. The widespread evidence for the presence of CO₂ in both the oceanic and continental upper mantle implies that such low degree SiO₂-poor carbonatitic melts are common in the mantle, despite the rarity of carbonatites themselves at the Earth's surface. Received: 9 April 1997 / Accepted: 25 November 1997     

A possible role for garnet pyroxenite in the origin of the “garnet signature” in MORB

 Geochemical data have been interpreted as requiring that a significant fraction of the melting in MORB source regions takes place in the garnet peridotite field, an inference that places the onset of melting at ≥80 km. However, if melting begins at such great depths, most models for melting of the suboceanic mantle predict substantially more melting than that required to produce the 7±1 km thickness of crust at normal ridges. One possible resolution of this conflict is that MORBs are produced by melting of mixed garnet pyroxenite/spinel peridotite sources and that some or all of the “garnet signature” in MORB is contributed by partial melting of garnet pyroxenite layers or veins, rather than from partial melting of garnet peridotite. Pyroxenite layers or veins in peridotite will contribute disproportionately to melt production relative to their abundance, because partial melts of pyroxenite will be extracted from a larger part of the source region than peridotite partial melts (because the solidus of pyroxenite is at lower temperature than that of peridotite and is encountered along an adiabat 15–25 km deeper than the solidus of peridotite), and because melt productivity from pyroxenite during upwelling is expected to be greater than that from peridotite (pyroxenite melt productivity will be particularly high in the region before peridotite begins melting, owing to heating from the enclosing peridotite). For reasonable estimates of pyroxenite and peridotite melt productivities, 15–20% of the melt derived from a source region composed of 5% pyroxenite and 95% peridotite will come from the pyroxenite. Most significantly, garnet persists on the solidus of pyroxenite to much lower pressures than those at which it is present on the solidus of peridotite, so if pyroxenite is present in MORB source regions, it will probably contribute a garnet signature to MORB even if melting only occurs at pressures at which the peridotite is in the spinel stability field. Partial melting of a mixed spinel peridotite/garnet pyroxenite mantle containing a few to several percent pyroxenite can explain quantitatively many of the geochemical features of MORB that have been attributed to the onset of melting in the stability field of garnet lherzolite, provided that the pyroxenite compositions are similar to the average composition of mantle-derived pyroxene-rich rocks worldwide or to reasonable estimates of the composition of subducted oceanic crust. Sm/Yb ratios of average MORB from regions of typical crustal thickness are difficult to reconcile with derivation by melting of spinel peridotite only, but can be explained if MORB sources contain ∼5% garnet pyroxenite. Relative to melting of spinel peridotite alone, participation of model pyroxenite in melting lowers aggregate melt Lu/Hf without changing Sm/Nd ratios appreciably. Lu/Hf-Sm/Nd systematics of most MORB can be accounted for by melting of a spinel peridotite/garnet pyroxenite mantle provided that the source region contains 3–6% pyroxenite with ≥20% modal garnet. However, Lu/Hf-Sm/Nd systematics of some MORB appear to require more complex melting regimes and/or significant isotopic heterogeneity in the source. Another feature of the MORB garnet signature, (²³⁰Th)/(²³⁸U)>1, can also be produced under these conditions, although the magnitude of (²³⁰Th)/(²³⁸U) enrichment will depend on the rate of melt production when the pyroxenite first encounters the solidus, which is not well-constrained. Preservation of high (²³⁰Th)/(²³⁸U) in aggregated melts of mixed spinel peridotite/garnet pyroxenite MORB sources is most likely if the pyroxenites have U concentrations similar to that expected in subducted oceanic crust or to pyroxenite from alpine massifs and xenoliths. The abundances of pyroxenite in a mixed source that are required to explain MORB Sm/Yb, Lu/Hf, and (²³⁰Th)/(²³⁸U) are all similar. If pyroxenite is an important source of garnet signatures in MORB, then geochemical indicators of pyroxenite in MORB source regions, such as increased trace element and isotopic variability or more radiogenic Pb or Os, should correlate with the strength of the garnet signature. Garnet signatures originating from melts of the garnet pyroxenite components of mixed spinel peridotite/garnet pyroxenite sources would also be expected to be stronger in regions of thin crust. Received: 15 February 1995/Accepted: 7 February 1996     

The role of oxidation-reduction and C-H-O fluids in determining melting conditions and magma compositions in the upper mantle

High pressure experimental studies of the melting of lherzolitic upper mantle in the absence of carbon and hydrogen have shown that the lherzolite solidus has a positive dP/dT and that the percentage melting increases quite rapidly above the solidus. In contrast, the presence of carbon and hydrogen in the mantle results in a region of ‘incipient’ melting at temperatures below the C,H-free solidus. In this region the presence or absence of melt and the composition of the melt are dependent on the amount and nature of volatiles, particularly the CO₂, H₂O, and CH₄ contents of the potential C-H-O fluid. Under conditions of low (IW to IW + 1 log unit atP ∼ 20–35kb), fluids such as CH₄+H₂O and CH₄+H₂ inhibit melting, having a low solubility in silicate melts. Under these conditions, carbon and hydrogen are mobile elements in the upper mantle. At slightly higher oxygen fugacity (IW+2 log units,P∼20–35 kb) fluids in equilibrium with graphite or diamond in peridotite C-H-O are extremely water-rich. Carbon is thus not mobile in the mantle in this range and the melting and phase relations for the upper mantle lherzolite approximate closely to the peridotite-H₂O system. Pargasitic amphibole is stable to solidus temperatures in fertile lherzolite compositions and causes a distinctive peridotite solidus, the ‘dehydration solidus’, with a marked change in slope (a ‘back bend’) at 29–30kb due to instability of pargasite at high pressure. Intersections of geothermal gradients with the peridotite-H₂O solidi define the boundary between lithosphere (subsolidus) and asthenosphere (incipient melt region). This boundary is thus sensitive to changes in [affecting CH₄:H₂O:CO₂ ratios] and to the amount of H₂O and carbon (CO₂, CH₄) present. At higher conditions (IW + 3 log units), CO₂-rich fluids occur at low pressures but there is a marked depression of the solidus at 20–21 kb due to intersection with the carbonation reaction, producing the low temperature solidus for dolomite amphibole lherzolite (T∼925°C, 21 to >31kb). Melting of dolomite (or magnesite) amphibole lherzolite yields primary sodic dolomitic carbonatite melt with low H₂O content, in equilibrium with amphibole garnet lherzolite. The complexity of melting in peridotite-C-H-O provides possible explanations for a wide range of observations on lithosphere/asthenosphere relations, on mantle melt and fluid compositions, and on processes of mantle metasomatism and magma genesis in the upper mantle.     

Anhydrous partial melting of an iron-rich mantle I: subsolidus phase assemblages and partial melting phase relations at 10 to 30 kbar

Anhydrous partial melting experiments, at 10 to 30 kbar from solidus to near liquidus temperature, have been performed on an iron-rich martian mantle composition, DW. The DW subsolidus assemblage from 5 kbar to at least 24 kbar is a spinel lherzolite. At 25 kbar garnet is stable at the solidus along with spinel. The clinopyroxene stable on the DW solidus at and above 10 kbar is a pigeonitic clinopyroxene. Pigeonitic clinopyroxene is the first phase to melt out of the spinel lherzolite assemblage at less than 20°C above the solidus. Spinel melts out of the assemblage about 50°C above the solidus followed by a 150° to 200°C temperature interval where melts are in equilibrium with orthopyroxene and olivine. The temperature interval over which pigeonitic clinopyroxene melts out of an iron-rich spinel lherzolite assemblage is smaller than the temperature interval over which augite melts out of an iron-poor spinel lherzolite assemblage. The dominant solidus assemblage in the source regions of the Tharsis plateau, and for a large percentage of the martian mantle, is a spinel lherzolite.     

Peridotite Melting at 1 GPa: Reversal Experiments on Partial Melt Compositions Produced by Peridotite-Basalt Sandwich Experiments

One of the goals of igneous petrology is to use the subtle andmore obvious differences in the geochemistry of primitive basaltsto place constraints on mantle composition, melting conditionsand dynamics of mantle upwelling and melt extraction. For thisgoal to be achieved, our first-order understanding of mantlemelting must be refined by high-quality, systematic data oncorrelated melt and residual phase compositions under knownpressures and temperatures. Discrepancies in earlier data onmelt compositions from a fertile mantle composition [MORB (mid-oceanridge basalt) Pyrolite mg-number 87] and refractory lherzolite(Tinaquillo Lherzolite mg-number 90) are resolved here. Errorsin earlier data resulted from drift of W/Re thermocouples at1 GPa and access of water, lowering liquidus temperatures by30–80°C. We demonstrate the suitability of the ‘sandwich’technique for determining the compositions of multiphase-saturatedliquids in lherzolite, provided fine-grained sintered oxidemixes are used as the peridotite starting materials, and thechanges in bulk composition are considered. Compositions ofliquids in equilibrium with lherzolitic to harzburgitic residueat 1 GPa, 1300–1450°C in the two lherzolite compositionsare reported. Melt compositions are olivine + hypersthene-normative(olivine tholeiites) with the more refractory composition producinga lower melt fraction (7–8% at 1300°C) compared withthe model MORB source (18–20% at 1300°C). KEY WORDS: mantle melting; sandwich experiments; reversal experiments; anhydrous peridotite melting; thermocouple oxidation; olivine geothermometry     

An absarokite from a phlogopite lherzolite source

An absarokite (SiO₂ 47.72 wt %, K₂O 3.41 wt %) occurs in the Katamata volcano, SW Japan. The rock carries phenocrysts of olivine, phlogopite, clinopyroxene, and hornblende. Chemical compositions of bulk rock (FeO^*/ MgO 0.73) and minerals (Mg-rich olivine and phlogopite, Cr-rich chromite) suggest that the absarokite is not differentiated. Melting experiments at high pressures on the Katamata absarokite have been conducted. The completely anhydrous absarokite melt coexists with olivine, orthopyroxene, and clinopyroxene at 1310° C and 1.0 GPa. The melt with 3.29 wt % of H₂O also coexists with the above three phases at 1230° C and 1.4 GPa; phlogopite appears at temperatures more than 80° C below the liquidus. On the other hand, the melt is not saturated with lherzolite minerals in the presence of 5.13 wt % of H₂O and crystallizes olivine and phlogopite as liquidus phases; the stability limit of phlogopite is little affected at least by the present variation of H₂O content in the absarokite melt. It is suggested that the absarokite magma was segregated from the upper mantle at 1170° C and 1.7 GPa leaving a phlogopite lherzolite as a residual material on the basis of the above experimental results and the petrographical observation that olivine and phlogopite crystallize at an earlier stage of crystallization sequence than clinopyroxene. The contribution of phlogopite at the stage of melting processes is also suggested by the geochemical characteristics that the absarokite is more enriched in Rb, K, and Ba and depleted in Ca and Na than a typical alkali olivine basalt from the same volcanic field.     

Melts in the mantle modeled in the system CaO-MgO-SiO2-CO2 at 2.7 GPa

The effect of CO₂ on mantle peridotites is modeled by experimental data for the system CaO-MgO-SiO₂-CO₂ at 2.7 GPa. The experiments provide isotherms for the vapor-saturated liquidus surface, bracket piercing points for field boundaries on the surface, and define the positions and compositions of isobaric invariant liquids on the boundaries (eutectics and peritectics). CO₂-saturated carbonatitic liquids (>80% carbonate) exist through approximately 200 °C above the solidus, with a transition to silicate liquids (>80% silicate) within ∼75 °C across a plateau on the liquidus. Carbonate-rich magmas cannot cross the silicate-carbonate liquidus field boundary, so the carbonate liquidus field is therefore a forbidden volume for liquid magmas. This confirms the fact that rounded, pure carbonates in mantle xenoliths cannot represent original liquids. A P-T diagram is constructed for the carbonation and melting reactions for mineral assemblages corresponding to lherzolite, harzburgite, websterite and wehrlite, with carbonate, CO₂ vapor (V), or both. The changing compositions of liquids in solidus reactions on the P-T diagram are illustrated by the changing compositions of eutectic and peritectic liquids on the liquidus surface. At an invariant point Q (∼2.8 GPa/1230 °C), all peridotite assemblages coexist with a calcite-dolomite solid solution (75 ± 5% CaCO₃) and a dolomitic carbonatite melt [57% CaCO₃ (CC), 33% MgCO₃ (MC), 10% CaMgSi₂O₆ (Di)], with 63% CC in the carbonate component. At higher pressures, dolomite-lherzolite, dolomite-harzburgite-V, and dolomite-websterite-V melt to yield similar liquids. Magnesian calcite-wehrlite is the only peridotite melting to carbonatitic liquids (more calcic) at pressures below Q (∼70 km). Dolomitic carbonatite magma rising through mantle to the near-isobaric solidus ledge near Q will begin to crystallize, releasing CO₂ (enhancing crack propagation), and metasomatizing lherzolite toward wehrlite. Received: 20 March 1998 / Accepted: 7 July 1999     

Stability and chemical composition of pargasitic amphibole in MORB pyrolite under upper mantle conditions

The stability field of pargasitic amphibole in a model mantle composition (MORB pyrolite) has been experimentally determined for a fixed water content. A solidus for a pargasite-bearing lherzolite has been defined at pressures below the limit of amphibole stability of 30 kbar at T = 925 °C. The maximum temperature for pargasitic amphibole in MORB pyrolite occurs at 1075 °C between P = 18 and 25 kbar. This maximum lies between that determined for a fertile peridotite composition (Hawaiian pyrolite) and a depleted peridotite composition (Tinaquillo lherzolite). A comparison of the new results with those from earlier studies suggests that the stability for a particular bulk H₂O content is mostly controlled by alkali content of the lherzolite composition. The systematic compositional variation of pargasitic amphibole as a function of pressure and temperature can be represented as an increase of the richterite component with increase in both pressure and temperature. For a given pressure the tschermakite component increases with increasing temperature. The compositions of coexisting clinopyroxenes also show a systematic variation with pressure and temperature. The phase relationships in MORB pyrolite combined with the modal abundance of coexisting phases show that the breakdown reactions of pargasitic amphibole occur continuously throughout the subsolidus region studied. The temperature stability limit of pargasitic amphibole coincides with the water-undersaturated solidus (amphibole-dehydration solidus) at pressures below 30 kbar. The experimental results are applicable to pargasitic amphibole-bearing natural peridotites. Cooling and decompression paths and heating events observed in natural peridotites can be interpreted from changes in the composition of pargasitic amphibole. The data are also applicable to a model for peridotite melting and hydration process in the subduction environment. Received: 27 October 1997 / Accepted: 6 November 1998     

Systematics of metal-silicate partitioning for many siderophile elements applied to Earth’s core formation

Superliquidus metal-silicate partitioning was investigated for a number of moderately siderophile (Mo, As, Ge, W, P, Ni, Co), slightly siderophile (Zn, Ga, Mn, V, Cr) and refractory lithophile (Nb, Ta) elements. To provide independent constrains on the effects of temperature, oxygen fugacity and silicate melt composition, isobaric (3 GPa) experiments were conducted in piston cylinder apparatus at temperature between 1600 and 2600 °C, relative oxygen fugacities of IW−1.5 to IW−3.5, and for silicate melt compositions ranging from basalt to peridotite. The effect of pressure was investigated through a combination of piston cylinder and multi-anvil isothermal experiments between 0.5 and 18 GPa at 1900 °C. Oxidation states of siderophile elements in the silicate melt as well as effect of carbon saturation on partitioning are also derived from these results. For some elements (e.g. Ga, Ge, W, V, Zn) the observed temperature dependence does not define trends parallel to those modeled using metal-metal oxide free energy data. We correct partitioning data for solute interactions in the metallic liquid and provide a parameterization utilized in extrapolating these results to the P-T-X conditions proposed by various core formation models. A single-stage core formation model reproduces the mantle abundances of several siderophile elements (Ni, Co, Cr, Mn, Mo, W, Zn) for core-mantle equilibration at pressures from 32 to 42 GPa along the solidus of a deep peridotitic magma ocean (∼3000 K for this pressure range) and oxygen fugacities relevant to the FeO content of the present-day mantle. However, these P-T-fO₂ conditions cannot produce the observed concentrations of Ga, Ge, V, Nb, As and P. For more reducing conditions, the P-T solution domain for single stage core formation occurs at subsolidus conditions and still cannot account for the abundances of Ge, Nb and P. Continuous core formation at the base of a magma ocean at P-T conditions constrained by the peridotite liquidus and fixed fO₂ yields concentrations matching observed values for Ni, Co, Cr, Zn, Mn and W but underestimates the core/mantle partitioning observed for other elements, notably V, which can be reconciled if accretion began under reducing conditions with progressive oxidation to fO₂ conditions consistent with the current concentration of FeO in the mantle as proposed by Wade and Wood (2005). However, neither oxygen fugacity path is capable of accounting for the depletions of Ga and Ge in the Earth’s mantle. To better understand core formation, we need further tests integrating the currently poorly-known effects of light elements and more complex conditions of accretion and differentiation such as giant impacts and incomplete equilibration.     

Melting of carbonated pelites at 8–13 GPa: generating K-rich carbonatites for mantle metasomatism

The melting behaviour of three carbonated pelites containing 0–1 wt% water was studied at 8 and 13 GPa, 900–1,850°C to define conditions of melting, melt compositions and melting reactions. At 8 GPa, the fluid-absent and dry carbonated pelite solidi locate at 950 and 1,075°C, respectively; >100°C lower than in carbonated basalts and 150–300°C lower than the mantle adiabat. From 8 to 13 GPa, the fluid-present and dry solidi temperatures then increase to 1,150 and 1,325°C for the 1.1 wt% H₂O and the dry composition, respectively. The melting behaviour in the 1.1 wt% H₂O composition changes from fluid-absent at 8 GPa to fluid-present at 13 GPa with the pressure breakdown of phengite and the absence of other hydrous minerals. Melting reactions are controlled by carbonates, and the potassium and hydrous phases present in the subsolidus. The first melts, which composition has been determined by reverse sandwich experiments, are potassium-rich Ca–Fe–Mg-carbonatites, with extreme K₂O/Na₂O wt ratios of up to 42 at 8 GPa. Na is compatible in clinopyroxene with D_\textNa^{\textcpx/\textcarbonatite} = 10-18 D_{\text{Na}}^{{{\text{cpx}}/{\text{carbonatite}}}} = 10{-}18 at the solidus at 8 GPa. The melt K₂O/Na₂O slightly decreases with increasing temperature and degree of melting but strongly decreases from 8 to 13 GPa when K-hollandite extends its stability field to 200°C above the solidus. The compositional array of the sediment-derived carbonatites is congruent with alkali- and CO₂-rich melt or fluid inclusions found in diamonds. The fluid-absent melting of carbonated pelites at 8 GPa contrasts that at ≤5 GPa where silicate melts form at lower temperatures than carbonatites. Comparison of our melting temperatures with typical subduction and mantle geotherms shows that melting of carbonated pelites to 400-km depth is only feasible for extremely hot subduction. Nevertheless, melting may occur when subduction slows down or stops and thermal relaxation sets in. Our experiments show that CO₂-metasomatism originating from subducted crust is intimately linked with K-metasomatism at depth of >200 km. As long as the mantle remains adiabatic, low-viscosity carbonatites will rise into the mantle and percolate upwards. In cold subcontinental lithospheric mantle keels, the potassic Ca–Fe–Mg-carbonatites may freeze when reacting with the surrounding mantle leading to potassium-, carbonate/diamond- and incompatible element enriched metasomatized zones, which are most likely at the origin of ultrapotassic magmas such as group II kimberlites.     

The effect of bulk composition on the solidus of carbonated eclogite from partial melting experiments at 3 GPa

To explore the effect of bulk composition on the solidus of carbonated eclogite, we determined near-solidus phase relations at 3 GPa for four different nominally anhydrous, carbonated eclogites. Starting materials (SLEC1, SLEC2, SLEC3, and SLEC4) were prepared by adding variable proportions and compositions of carbonate to a natural eclogite xenolith (66039B) from Salt Lake crater, Hawaii. Near-solidus partial melts for all bulk compositions are Fe–Na calcio-dolomitic and coexist with garnet + clinopyroxene + ilmenite ± calcio-dolomitic solid solution. The solidus for SLEC1 (Ca#=100 × molar Ca/(Ca + Mg + Fe_T)=32, 1.63 wt% Na₂O, and 5 wt% CO₂) is bracketed between 1,050°C and 1,075°C (Dasgupta et al. in Earth Planet Sci Lett 227:73–85, 2004), whereas initial melting for SLEC3 (Ca# 41, 1.4 wt% Na₂O, and 4.4 wt% CO₂) is between 1,175°C and 1,200°C. The solidus for SLEC2 (Ca# 33, 1.75 wt% Na₂O, and 15 wt% CO₂) is estimated to be near 1,100°C and the solidus for SLEC3 (Ca# 37, 1.47 wt% Na₂O, and 2.2 wt% CO₂) is between 1,100°C and 1,125°C. Solidus temperatures increase with increasing Ca# of the bulk, owing to the strong influence of the calcite–magnesite binary solidus-minimum on the solidus of carbonate bearing eclogite. Bulk compositions that produce near-solidus crystalline carbonate closer in composition to the minimum along the CaCO₃-MgCO₃ join have lower solidus temperatures. Variations in total CO₂ have significant effect on the solidus if CO₂ is added as CaCO₃, but not if CO₂ is added as a complex mixture that maintains the cationic ratios of the bulk-rock. Thus, as partial melting experiments necessarily have more CO₂ than that likely to be found in natural carbonated eclogites, care must be taken to assure that the compositional shifts associated with excess CO₂ do not unduly influence melting behavior. Near-solidus dolomite and calcite solid solutions have higher Ca/(Ca + Mg) than bulk eclogite compositions, owing to Ca–Mg exchange equilibrium between carbonates and silicates. Carbonates in natural mantle eclogite, which have low bulk CO₂ concentration, will have Ca/Mg buffered by reactions with silicates. Consequently, experiments with high bulk CO₂ may not mimic natural carbonated eclogite phase equilibria unless care is taken to ensure that CO₂ enrichment does not result in inappropriate equilibrium carbonate compositions. Compositions of eclogite-derived carbonate melt span the range of natural carbonatites from oceanic and continental settings. Ca#s of carbonatitic partial melts of eclogite vary significantly and overlap those of partial melts of carbonated lherzolite, however, for a constant Ca-content, Mg# of carbonatites derived from eclogitic sources are likely to be lower than the Mg# of those generated from peridotite.     

Absarokites from the western Mexican Volcanic Belt: constraints on mantle wedge conditions

We have investigated the near liquidus phase relations of a primitive absarokite from the Mascota region in western Mexico. Sample M.102 contains ~11.6 wt% MgO, Mg#=0.73 and the lava contains Fo₉₀ olivine phenocrysts, indicating near equilibrium with the mantle. High-pressure experiments on a synthetic analogue of the absarokite composition containing low and high H₂O abundances of (~2 and ~5 wt%, respectively) were performed in a piston cylinder apparatus over the pressure range of 1.2 to 2.0 GPa. The composition containing ~2 wt% H₂O is multiply saturated with olivine and orthopyroxene at 1.6 GPa and 1,400 °C. At the same pressure, clinopyroxene appears 30 °C below the liquidus. At an H₂O content of ~5 wt% the multiple saturation with olivine and orthopyroxene occurs at 1.7 GPa and 1,300 °C. Assuming a batch-melting process, we suggest that the primitive absarokite was segregated from a depleted lherzolite or harzburgite residue at ~50 km, placing the depth of origin well within the mantle wedge beneath the Jalisco Block. A low degree (<5 %wt%) batch-melt of an original metasomatized depleted lherzolite or harzburgite source would contain the observed trace element abundances found in M.102. The liquidus phase relations are not consistent with the presence of non-peridotitic veins at the depth of last equilibration. Therefore, we propose that the Mascota absarokites segregated at an apparent melt fraction of less than 5% from a depleted peridotitic source. Melting first began at a greater depth as a small degree H₂O- and trace element- rich melt of a metasomatized peridotite that ascended into the overlying wedge and re-equilibrated with shallower, hotter mantle.Editorial responsibility: J. Hoefs     

Distribution of REE between clinopyroxene and basaltic melt along a mantle adiabat: effects of major element composition, water, and temperature

The distribution of rare earth elements (REE) between clinopyroxene (cpx) and basaltic melt is important in deciphering the processes of mantle melting. REE and Y partition coefficients from a given cpx-melt partitioning experiment can be quantitatively described by the lattice strain model. We analyzed published REE and Y partitioning data between cpx and basaltic melts using the nonlinear regression method and parameterized key partitioning parameters in the lattice strain model (D ₀, r ₀ and E) as functions of pressure, temperature, and compositions of cpx and melt. D ₀ is found to positively correlate with Al in tetrahedral site (Al ^T ) and Mg in the M2 site (Mg^M2) of cpx and negatively correlate with temperature and water content in the melt. r ₀ is negatively correlated with Al in M1 site (Al^M1) and Mg^M2 in cpx. And E is positively correlated with r ₀. During adiabatic melting of spinel lherzolite, temperature, Al ^T , and Mg^M2 in cpx all decrease systematically as a function of pressure or degree of melting. The competing effects between temperature and cpx composition result in very small variations in REE partition coefficients along a mantle adiabat. A higher potential temperature (1,400°C) gives rise to REE partition coefficients slightly lower than those at a lower potential temperature (1,300°C) because the temperature effect overwhelms the compositional effect. A set of constant REE partition coefficients therefore may be used to accurately model REE fractionation during partial melting of spinel lherzolite along a mantle adiabat. As cpx has low Al and Mg abundances at high temperature during melting in the garnet stability field, REE are more incompatible in cpx. Heavy REE depletion in the melt may imply deep melting of a hydrous garnet lherzolite. Water-dependent cpx partition coefficients need to be considered for modeling low-degree hydrous melting.     

Melting Behaviour of Model Lherzolite in the System CaO-MgO-Al2O3-SiO2-FeO at 0{middle dot}7-2{middle dot}8 GPa

Fe–Mg exchange is the most important solid solution involvedin partial melting of spinel lherzolite, and the system CaO–MgO–Al₂O₃–SiO₂–FeO(CMASF) is ideally suited to explore this type of exchange duringmantle melting. Also, if primary mid-ocean ridge basalts arelargely generated in the spinel lherzolite stability field bynear-fractional fusion, then Na and other highly incompatibleelements will early on become depleted in the source, and themelting behaviour of mantle lherzolite should resemble the meltingbehaviour of simplified lherzolite in the CMASF system. We havedetermined the isobarically univariant melting relations ofthe lherzolite phase assemblage in the CMASF system in the 0·7–2·8GPa pressure range. Isobarically, for every 1 wt % increasein the FeO content of the melt in equilibrium with the lherzolitephase assemblage, the equilibrium temperature is lower by about3–5°C. Relative to the solidus of model lherzolitein the CaO–MgO–Al₂O₃–SiO₂ system, melt compositionsin the CMASF system are displaced slightly towards the alkalicside of the basalt tetrahedron. The transition on the solidusfrom spinel to plagioclase lherzolite has a positive Clapeyronslope with the spinel lherzolite assemblage on the high-temperatureside, and has an almost identical position in P–T spaceto the comparable transition in the CaO–MgO–Al₂O₃–SiO₂–Na₂O(CMASN) system. When the compositions of all phases are describedmathematically and used to model the generation of primary basalts,temperature and melt composition changes are small as percentmelting increases. More specifically, 10% melting takes placeover 1·5–2°C, melt compositions are relativelyinsensitive to the degree of melting and bulk composition, andequilibrium and near-fractional melting yield similar melt compositions.FeO and MgO are the oxides that exhibit the greatest changein the melt with degree of melting and bulk composition. Theamount of FeO decreases with increasing degree of melting, whereasthe amount of MgO increases. The coefficients for Fe–Mgexchange between the coexisting crystalline phases and melt,K_dFe–Mg^xl–liq, show a relatively simple and predictablebehaviour with pressure and temperature: the coefficients forolivine and spinel do not show significant dependence on temperature,whereas the coefficients for orthopyroxene and clinopyroxeneincrease with pressure and temperature. When melting of lherzoliteis modeled in the CMASF system, a strong linear correlationis observed between the mg-number of the lherzolite and themg-number of the near-solidus melts. Comparison with meltingin the CMASN system indicates that Na₂O has a strong effecton lherzolite melting behaviour only at small degrees of melting. KEY WORDS: CMASF; lherzolite solidus; mantle melting     

Experiments on melt–rock reaction in the shallow mantle wedge

This experimental study simulates the interaction of hotter, deeper hydrous mantle melts with shallower, cooler depleted mantle, a process that is expected to occur in the upper part of the mantle wedge. Hydrous reaction experiments (~6 wt% H₂O in the melt) were conducted on three different ratios of a 1.6 GPa mantle melt and an overlying 1.2 GPa harzburgite from 1060 to 1260 °C. Reaction coefficients were calculated for each experiment to determine the effect of temperature and starting bulk composition on final melt compositions and crystallizing assemblages. The experiments used to construct the melt–wall rock model closely approached equilibrium and experienced <5% Fe loss or gain. Experiments that experienced higher extents of Fe loss were used to critically evaluate the practice of “correcting” for Fe loss by adding iron. At low ratios of melt/mantle (20:80 and 5:95), the crystallizing assemblages are dunites, harzburgites, and lherzolites (as a function of temperature). When the ratio of deeper melt to overlying mantle is 70:30, the crystallizing assemblage is a wehrlite. This shows that wehrlites, which are observed in ophiolites and mantle xenoliths, can be formed by large amounts of deeper melt fluxing though the mantle wedge during ascent. In all cases, orthopyroxene dissolves in the melt, and olivine crystallizes along with pyroxenes and spinel. The amount of reaction between deeper melts and overlying mantle, simulated here by the three starting compositions, imposes a strong influence on final melt compositions, particularly in terms of depletion. At the lowest melt/mantle ratios, the resulting melt is an extremely depleted Al-poor, high-Si andesite. As the fraction of melt to mantle increases, final melts resemble primitive basaltic andesites found in arcs globally. An important element ratio in mantle lherzolite composition, the Ca/Al ratio, can be significantly elevated through shallow mantle melt–wall rock reaction. Wall rock temperature is a key variable; over a span of <80 °C, reaction with deeper melt creates the entire range of mantle lithologies from a depleted dunite to a harzburgite to a refertilized lherzolite. Together, the experimental phase equilibria, melt compositions, and reaction coefficients provide a framework for understanding how melt–wall rock reaction occurs in the natural system during melt ascent in the mantle wedge.     

Anhydrous melting of peridotite at 0–15 Kb pressure and the genesis of tholeiitic basalts

The anhydrous melting behaviour of two synthetic peridotite compositions has been studied experimentally at temperatures ranging from near the solidus to about 200° C above the solidus within the pressure range 0–15 kb. The peridotite compositions studied are equivalent to Hawaiian pyrolite and a more depleted spinel lherzolite (Tinaquillo peridotite) and in both cases the experimental studies used peridotite –40% olivine compositions. Equilibrium melting results in progressive elimination of phases with increasing temperature. Four main melting fields are recognized; from the solidus these are: olivine (ol)+orthopyroxene (opx)+clinopyroxene (cpx)+Al-rich phase (plagioclase at low pressure, spinel at moderate pressure, garnet at high pressure)+liquid (L); ol+opx+cpx+Cr-spinel+L; ol+opx+Cr-spinel +L: ol±Cr-spinel+L. Microprobe analyses of the residual phases show progressive changes to more refractory compositions with increasing proportion of coexisting melt i.e. increasing Mg/(Mg+Fe) and Cr/(Cr+Al) ratios, decreasing Al₂O₃, CaO in pyroxene.The degree of melting, established by modal analysis, increases rapidly immediately above the solidus (up to 10% melting occurs within 25°–30° C of the solidus), and then increases in roughly linear form with increasing temperature.Equilibrium melt compositions have been calculated by mass balance using the compositions and proportions of residual phases to overcome the problems of iron loss and quench modification of the glass. Compositions from the melting of pyrolite within the spinel peridotite field (i.e. 15 kb) range from alkali olivine basalt (<15% melting) through olivine tholeiite (20–30% melting) and picrite to komatiite (40–60% melting). Melting in the plagioclase peridotite field produces magnesian quartz tholeiite and olivine-poor tholeiite and, at higher degrees of melting (30–40%), basaltic or pyroxenitic komatiite. Melts from Tinaquillo lherzolite are more silica saturated than those from pyrolite for similar degrees of partial melting, and range from olivine tholeiite through tholeiitic picrite to komatiite for melting in the spinel peridotite field.The equilibrium melts are compared with inferred primary magma compositions and integrated with previous melting studies on basalts. The data obtained here and complementary basalt melting studies do not support models of formation of oceanic crust in which the parental magmas of common mid-ocean ridge basalts (MORB) are attributed to segregation from source peridotite at shallow depths ( 25 km) to leave residual harzburgite. Liquids segregating from peridotite at these depths are more silica-rich than common MORB.